EP3058047B1 - Quaternäre n-alkyl-n'-poly(oxyalkyl)hexahydropyrimidin-ammoniumsalze und verwendung davon als korrosionsinhibitoren - Google Patents

Quaternäre n-alkyl-n'-poly(oxyalkyl)hexahydropyrimidin-ammoniumsalze und verwendung davon als korrosionsinhibitoren Download PDF

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Publication number
EP3058047B1
EP3058047B1 EP14781811.6A EP14781811A EP3058047B1 EP 3058047 B1 EP3058047 B1 EP 3058047B1 EP 14781811 A EP14781811 A EP 14781811A EP 3058047 B1 EP3058047 B1 EP 3058047B1
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Prior art keywords
alkyl
compounds
corrosion
poly
oxyalkyl
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EP14781811.6A
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French (fr)
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EP3058047A1 (de
Inventor
Dirk Leinweber
Hannah Benson
Nihal Obeyesekere
Thenuka Ariyaratna
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Clariant International Ltd
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Clariant International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/04—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Definitions

  • Corrosion is a serious and challenging problem in the oil and gas industry and its prevention is acute in offshore operations.
  • Water, acidic gases such as hydrogen sulfide and carbon dioxide, organic acids, and oxygen contribute to the corrosion of mild steel, and other types of alloys used in the oil and gas industry.
  • Corrosion can cause oil and gas to leak from flowlines which can lead to explosions, accidents, and environmental disasters.
  • Corrosion inhibitors are essential for preventing uncontrolled discharge of oil and /or gas into the environments surrounding the flowlines.
  • Corrosion inhibitors are either water-soluble or oil soluble chemical compounds. When added in small quantities to an aggressive medium, these chemicals inhibit corrosion by changing the surface conditions of the metal.
  • the major factors controlling corrosion rates are CO 2 , H 2 S, S, polysulfides, organic acids, composition of liquids, flow conditions, inorganic anions, such as chlorides, oxygen, and temperature.
  • Sweet systems that contain very little or no H 2 S can be treated easily by using corrosion inhibitors. Mitigating corrosion in systems that produce high levels of H 2 S with CO 2 are difficult because these systems can produce elemental sulfur and polysulfides, which tend to cause localized rather than general corrosion.
  • US2004/0169161 A1 discloses the use of doubly alkoxylated quaternary compounds as corrosion inhibitors with improved water solubility and improved film persistence.
  • US2005/0156137 A1 discloses nitrogen-containing hydroxyethyl substituted compounds as corrosion inhibitors to be used under sweet-well conditions as well as under sour-well conditions.
  • the problem to be solved by innovation was to synthesize improved corrosion inhibitors particularly suitable for sour gas environments.
  • WO 2009/064719 teaches an imidazoline-based foaming composition comprising:
  • EP-A-0156631 teaches a corrosion inhibitor characterized in that it is the reaction product of
  • N-alkyl-N'-poly(oxyalkyl)hexahydropyrimidine-quaternary ammonium salts give excellent corrosion-protection for water/oil emulsions as they are present in petroleum.
  • these compounds show improved corrosion inhibition properties when compared with conventional sour gas corrosion inhibitors such as alkyl pyridine quaternary compounds.
  • the invention provides N-alkyl-N'-poly(oxyalkyl)hexahydropyrimidine-quaternary ammonium salts of the formulae (Ia) - (Ic) in which
  • a process for inhibiting corrosion of metal comprises bringing the metal into contact with one or more of the compounds according to the formulae (Ia) - (Ic).
  • the process is preferably applied to metal which is in contact with sour gas during crude oil or natural gas production or processing.
  • R 1 is preferably a radical of a naturally occurring fatty acid. Since the amines which are used in the synthesis of the compounds (Ia) to (Ic) and in which R 1 is an alkyl or alkenyl group are generally random mixtures of homologs and also of isomers, R 1 will usually be a mixture of different alkyl and/or alkenyl groups having various chain lengths. The number of carbon atoms given for R 1 shall therefore be understood as an average number.
  • R 1 is an alkyl or alkenyl group having from 8 to 24 carbon atoms, in particular having from 10 to 18 carbon atoms, especially those having from 12 to 18 carbon atoms.
  • Particularly advantageous radicals R 1 are those which can be traced back to the C 10 fraction, the C 10 /C 12 fraction, the, the C 12 /C 14 , or the C 16 /C 18 fractions of a primary amine.
  • straight-chain or branched alkyl and alkenyl groups R 1 which may be mentioned are: n-octyl, 2-ethylhexyl, n- and iso-nonyl, n- and iso-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, oleyl, linoleyl, linolenyl and behenyl.
  • the 1,2-alkylene group A has preferably 2 to 5 carbon atoms
  • the 1,2-alkylene group A is preferably an ethylene group or a propylene, 1,2-butylene or 2,3-butylene group.
  • each group A can also be a random mixture of a plurality of the specified 1,2-alkylene groups, mixtures of ethylene and propylene units being preferred.
  • the degree of alkoxylation p is between 1 and 50, preferably from 3 to 35, in particular from 5 to 15.
  • the values of p are usually averages.
  • R 3 is preferably methyl.
  • the counterion X - is, in a preferred embodiment and halogenide-ion, an organo sulfate R-O-SO 3 - or an organo carbonate R-O-CO 2 - .
  • it is chloride, bromide, iodide, methyl sulfate, ethyl sulfate or methyl carbonate.
  • X does not mean chloride when A means ethylene, R 2 means hydrogen and R 3 means methyl.
  • X does not mean chloride when A means ethylene.
  • R 2 means hydrogen, R 3 means methyl and R 1 is a tallow fatty residue.
  • the tallow fatty residue is a mixture of aliphatic hydrocarbons having the following composition, according to Ullmann's Encyclopedia of Industrial Chemistry, 2012: (percentages are wt.-%).
  • the compounds of the formulae (Ia) -(Ic) of the invention are generally obtained by N-alkylation of N-alkyl-N'-poly(oxyalkyl)-hexahydropyrimidines of the formula (II) whose preparation is described in US-005530131A .
  • the N-alkylation of the compounds of the formula (II) is carried out by methods known per se.
  • N-alkylating agents are for example Dimethyl sulfate, Diethyl sulfate, Dimethyl carbonate, Methyl iodide, Methyl chloride, allyl bromide or benzyl chloride.
  • N-alkyl-N'-poly(oxyalkyl)-hexahydropyrimidine and N-alkylating agent are reacted in equimolar amounts at temperatures in the range from 50 - 85 °C.
  • the N-alkyl-N'-poly(oxyalkyl)-hexahydropyrimidine is initially charged, heated to 50 - 60 °C and the N-alkylating agent is added.
  • reaction is exothermic and it should be avoided that the reaction mixture is heated to > 85 °C.
  • the reaction mixture is stirred, preferably at 80 °C, in order to obtain complete conversion to the desired product of the formulae (Ia) -(Ic) or product mixture thereof.
  • N-alkyl-N'-poly(oxyalkyl)-hexahydropyrimidine N-alkyl-N'-poly(oxyalkyl)-hexahydropyrimidine
  • substances of the formulae (Ia) - (Ic) is obtained.
  • equimolar means one mole N-alkylating agent per mole of starting material.
  • the compounds according to the invention comprise the compounds of formulae (Ia) and (Ib) and the ratio of compounds (Ia) and (Ib) is from 1 : 1.9 to 1.9 : 1, preferably 1 : 0.8 to 0.8 : 1 by weight.
  • the preparation of the substances of the formula (I) is preferably carried out under a stream of inert gas, preferably a stream of nitrogen.
  • the products of the formulae (Ia) - (Ic) are generally obtained in good yield and with high degree of purity.
  • the substances of the formulae (Ia) - (Ic) and mixtures thereof are suitable as corrosion inhibitors, in particular in petroleum extraction and processing plants which come into contact with salt water.
  • the amounts of these compounds used as corrosion inhibitors are from 1 to 200, preferably from 5 to 50, mg per liter of corrosive liquid. Since the compounds of the invention are usually prepared as highly viscous liquids, they are in practice normally used as a 20 - 50 % by weight strength solution, for example in water, glycols, glycol ethers, alcohols and other suitable solvents. These solutions can also include other corrosion-inhibiting active ingredients and also emulsifiers, antifoaming agents and further customary additives which improve the useful properties of the product being applied.
  • the LPR bubble tests were conducted in 1 L Pyrex glass vessels that were continuously purged with 200 ppm H 2 S gas (contained in an oxygen free CO 2 / N 2 gas matrix) and heated to 66 °C.
  • the testing solution comprised 900 mL of synthetic brine (Brine composition listed in Table 1) and deaerated overnight with CO 2 gas prior to saturation with 200 ppm H 2 S gas just before testing.
  • Working electrodes made from 1018 carbon steel (CS) with a surface area of 4.785 cm 2 were polished with 600 grit silicon carbide paper and rinsed in acetone prior to insertion into the testing solution.
  • a magnetic stir bar and hot plate combination was used to agitate and monitor heating of the solution for the duration of the tests.
  • Flow meters were used to ensure the H 2 S flow rates were identical between all cells.
  • Linear polarization resistance (LPR) measurements were made with a Gamry electrochemical measurement system.
  • a CS 1018 electrode was used as a pseudo-reference and a graphite rod was used as the counter electrode.
  • the chemicals were added at 10 ppm based on the total solution volume (900 mL) after the baseline corrosion rates were monitored for continuity.
  • CW 1112 is an alkyl pyridine quaternary ammonium chloride and a known corrosion inhibitor for sour corrosion.
  • the N-alkyl-N'-poly(oxyalkyl)hexahydropyrimidine-quaternary ammonium salt derivatives were tested against the benchmark products. The chemicals performed in a superior manner to the comparative chemicals.
  • Autoclaves equipped with rotating cage were used to simulate the high shear conditions for the purpose of evaluating system corrosivity as well as inhibitor performance.
  • the test solution consisting of 800 mL of synthetic brine was deaerated with CO 2 overnight before pressurizing into the autoclaves using CO 2 .
  • Three weight loss corrosion coupons fixed on the rotating cage were used in each autoclave. The pit formation and pit density were analyzed by a high-powered microscope. General corrosion rates were calculated by weight loss measurement. Test conditions are summarized below.
  • Table 3 Weight Loss Analyses For Sour Rotating Cage Autoclave Testing and Localized Corrosion in the Presence of Example 5 and Comparative Samples Product
  • Coupon Number Weight (g) Weight Loss (g) Average Corrosion Rate (mpy) Average Pit Frequency (>10 ⁇ m)
  • Coupon Number Weight (g) Weight Loss (g) Average Corrosion Rate (mpy) Average Pit Frequency (>10 ⁇ m)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Claims (10)

  1. Quaternäre N-Alkyl-N'-poly(oxyalkyl)hexahydropyrimidin-Ammoniumsalze der Formeln (Ia)-(Ic),
    Figure imgb0019
    Figure imgb0020
     wobei
    R1 C8-C30-Alkyl oder C8-C30-Alkenyl ist,
    R2 Wasserstoff, C1-C3-Alkyl, -COOH oder eine Gruppe ausgewählt aus den Formeln
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
     ist, wobei
    die Bindung über die Valenz, die den B-Rest enthält, erfolgt,
    B eine Einfachbindung oder eine C1- bis C3-Alkylengruppe ist,
    R3 C1-C4-Alkyl, Vinyl, Allyl oder Benzyl ist,
    X- ein Gegenion ist,
    A eine 1,2-Alkylengruppe mit von 2 bis 10 Kohlenstoffatomen ist und
    p eine Zahl von 1 bis 50 ist.
  2. Verbindungen gemäß Anspruch 1, wobei R1 C9-C24-Alkyl oder C9-C24-Alkenyl ist.
  3. Verbindungen gemäß Anspruch 1, wobei R3 Methyl ist.
  4. Verbindungen gemäß Anspruch 1, wobei R2 Wasserstoff ist.
  5. Verbindungen gemäß Ansprüchen 1-4, wobei A Ethylen ist.
  6. Verbindungen gemäß Ansprüchen 1-5, wobei der Grad der Ethoxylierung p im Mittel zwischen 5 und 15 beträgt.
  7. Verbindungen gemäß Ansprüchen 1-6, umfassend Verbindungen der Formel (Ia) und (Ib) und wobei das Verhältnis der Verbindungen (Ia) und (Ib) von 1:1,9 bis 1,9:1 nach Gewicht beträgt.
  8. Verwendung von Verbindungen gemäß Ansprüchen 1-7 als Korrosionshemmer oder in Korrosionshemmer-Formulierungen.
  9. Verfahren zum Hemmen der Korrosion von Metall, wobei das Verfahren Inkontaktbringen des Metalls mit einer oder mehreren der Verbindungen gemäß Ansprüchen 1 bis 7 umfasst.
  10. Verfahren gemäß Anspruch 9, wobei das Metall während Rohöl- oder Erdgasförderung oder -verarbeitung in Kontakt mit Sauergas steht.
EP14781811.6A 2013-10-16 2014-09-22 Quaternäre n-alkyl-n'-poly(oxyalkyl)hexahydropyrimidin-ammoniumsalze und verwendung davon als korrosionsinhibitoren Ceased EP3058047B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/055,644 US9334243B2 (en) 2013-10-16 2013-10-16 N-alkyl-N′-poly(oxyalkyl)hexahydropyrimidine-quaternary ammonium salts and the use thereof as corrosion inhibitors
PCT/EP2014/002565 WO2015055275A1 (en) 2013-10-16 2014-09-22 N-alkyl-n'-poly(oxyalkyl)hexahydropyrimidine-quatenary ammonium salts and the use thereof as corrosion inhibitors

Publications (2)

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EP3058047A1 EP3058047A1 (de) 2016-08-24
EP3058047B1 true EP3058047B1 (de) 2017-08-16

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US (1) US9334243B2 (de)
EP (1) EP3058047B1 (de)
CN (1) CN105247008A (de)
BR (1) BR112015028008A2 (de)
CA (1) CA2927648A1 (de)
EA (1) EA029980B1 (de)
WO (1) WO2015055275A1 (de)

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US11897796B2 (en) * 2020-01-23 2024-02-13 Championx Usa Inc. Compositions of heterocyclic compounds and uses as sulfidogenesis inhibitors

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Publication number Priority date Publication date Assignee Title
US4100100A (en) 1977-03-28 1978-07-11 The Dow Chemical Company Cobalt-containing inhibitor for sour gas conditioning solutions
EP0156631A3 (de) * 1984-03-29 1987-04-01 The Dow Chemical Company Korrosionsinhibitoren
DE4316374A1 (de) * 1993-05-15 1994-11-17 Hoechst Ag N-Alkyl-N' -poly(oxyalkyl)hexahydropyrimidine
DE10134226A1 (de) * 2001-07-13 2003-02-06 Clariant Gmbh Korrosionsinhibitoren mit verbesserter Wasserlöslichkeit und erhöhter Filmpersistenz
SE523240C2 (sv) 2001-12-12 2004-04-06 Akzo Nobel Nv Användning av hydroxyetylsubstituerad amin som korrosionsinhibitor i saltvattenhaltig miljö i oljefältsapplikationer
US8551925B2 (en) * 2007-11-15 2013-10-08 Nalco Company Imidazoline-based heterocyclic foamers for downhole injection

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EA201690045A1 (ru) 2016-05-31
US9334243B2 (en) 2016-05-10
US20150104349A1 (en) 2015-04-16
CA2927648A1 (en) 2015-04-23
EP3058047A1 (de) 2016-08-24
EA029980B1 (ru) 2018-06-29
BR112015028008A2 (pt) 2017-07-25
CN105247008A (zh) 2016-01-13
WO2015055275A1 (en) 2015-04-23

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